GGA+U calculations

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It is well-known that first principles calculations within the local density approximation (LDA) or generalized gradient approximation (GGA) lead to considerable error in calculated redox reaction energies of many transition metal compounds. This error arises from the self-interaction error in LDA and GGA, which is not canceled out in redox reactions where an electron is transferred between significantly different environments, such as between a metal and a transition metal or between a transition metal and oxygen. Extensive discussion of this issue can be found in the following works.[1][2][3][4]

In the Materials Project, we have calibrated U values for many transition metals of interest using the approach outlined in Wang et al.'s work[3]. At the present moment, U values have been calibrated for transition metal oxide systems only. The choice of systems to which we apply U was largely determined by our experience and by systematic benchmarking. It is very likely that we will expand calibration of U values to more chemical systems in the future.

Calibration of U values

The U values were obtained by fitting to experimental binary formation enthalpies as described in Wang et al.'s work, which is simple and accurately reproduces phase stabilities. A least squares method of obtaining the correct U value was used, as follows:

  1. For each non-overlapping formation energy reaction considered, we find the region where the formation energy error passes zero. For the V-O system, this includes the following:
    1. 2 V2O3 + O2 → 4 VO2
    2. 4VO2 + O2 → 2 V2O5
  2. For each formation energy region identified, we fit the linear equation 
\begin{align}
\mbox{Error/redox} & = m U + c
\end{align}
to the final U range. In the case of V, we will have two sets of (m,c).
  3. We find the U value that minimizes the sum of square Error / Redox.
  4. In the case of V, we get a U value of 3.25.

U values

The full list of U values used is described in the table below. For oxide containing any of the elements, both GGA and GGA+U calculations were performed.

Calibrated U values for Transition Metals
Element System Fitting Reaction Redox Couple Calibrated U (eV) Comments
Co Oxides 6 CoO + O2 → 2 Co3O4 Co2+ → Co2.67+ 3.32
Cr Oxides 2/3 Cr2O3 + O2 → 4/3 CrO3 Cr3+ → Cr6+ 3.7
Fe Oxides 6 FeO + O2 → 2 Fe3O4
4 Fe3O4 + O2 → 6 Fe2O3
Fe2+ → Fe2.67+
Fe2.67+ → Fe3+
5.3
Mn Oxides 6 MnO + O2 → 2 Mn3O4
Mn3O4 + O2 → 3 MnO2
Mn2+ → Mn2.67+
Mn2.67+ → Mn4+
3.9 Mn2O3 was explicitly excluded from calibration set
due to the large number of atoms in its unit cell.
Mo Oxides 2 MoO2 + O2 → 2 MoO3 Mo4+ → Mo6+ 4.38
Ni Oxides Li2O + NiO + O2 → LiNiO2 Ni2+ → Ni3+ 6.2 Binary formation energies are not readily available for the Ni.
The Ni U calibration was performed using a ternary oxide formation energy.[5]
V Oxides 2 V2O3 + O2 → 4 VO2
4 VO2 + O2 → 2 V2O5
V3+ → V4+
V4+ → V5+
3.25 VO was explicitly excluded from calibration set
due to its known metallic nature.
W Oxides 2 WO2 + O2 → 2 WO3 W4+ → W6+ 6.2

Caveats

The U values are calibrated for phase stability analyses, and should be used with care if applied to obtain other properties such as band structures. Also, the U values depend on the pseudopotential used. A discussion of the pseudopotentials used in the Materials Project can be found here.

References

  1. F. Zhou, M. Cococcioni, C. A. Marianetti, D. Morgan and G. Ceder. First-principles prediction of redox potentials in transition-metal compounds with LDA+U. Physical Review B, 2004, 70, 235121. doi:10.1103/PhysRevB.70.235121
  2. M. Cococcioni, S. de Gironcoli, Linear response approach to the calculation of the effective interaction parameters in the LDA+U method. Physical Review B, 2005, 71, 035105. doi:10.1103/PhysRevB.71.035105
  3. 3.0 3.1 L. Wang, T. Maxisch, & G. Ceder. Oxidation energies of transition metal oxides within the GGA+U framework. Physical Review B. 2006, 73, 195107, doi:10.1103/PhysRevB.73.195107
  4. A. Jain, G. Hautier, S. P. Ong, C. Moore, C. Fischer, K. A. Persson, & G. Ceder. Formation enthalpies by mixing GGA and GGA + U calculations. Physical Review B, 2011, 84(4), 045115. doi:10.1103/PhysRevB.84.045115
  5. M. Wang, A. Navrotsky Enthalpy of formation of LiNiO2, LiCoO2 and their solid solution, LiNi1-xCoxO2, Solid State Ionics, vol. 166, no. 1-2, pp. 167-173, Jan. 2004.

Authors

  1. Shyue Ping Ong